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Efficient Synthesis of All-Carbon Quaternary Centers via the Conjugate Addition of Functionalized Monoorganozinc Bromides
Published on: May 26, 2019
Zirconium/Nickel-Mediated One-Pot Ketone Synthesis
Yanran Ai1, Ning Ye1, Qiaoyi Wang1
1Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA, 02138, USA.
Abstract:
A zirconium/nickel-mediated one-pot synthesis of ketones is reported. In the presence of Zn or Mn, Cp2 ZrCl2 was found to dramatically accelerate the coupling and suppress side product formation via an I→SPy displacement at the same time. Unlike Zn/Pd- and Fe/Cu-mediated one-pot ketone syntheses, the new method is effective for nucleophiles bearing OR or equivalent functional groups at the α-position. A mechanism comprising a nickel catalytic cycle, a zirconium catalytic cycle, and Zr→Ni transmetalation is proposed, and Cp2 ZrCl2 and/or low-valent Zr species are suggested to play crucial dual roles.
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